Color photographic process

ABSTRACT

In a process for processing a color photographic material using a waterproof support, the stability of color images formed is remarkably improved by processing the color photographic material, after color development, in a blix-stabilizing bath containing a Fe (III)- organic acid complex salt, a solvent for silver halide, and a water-soluble compound having an aldehyde group or a methylol group.

United States Patent [1 1 Yamaguchi 1 Apr. 22, 1975 1 COLORPI-IOTOGRAPI-IIC PROCESS [75] Inventor:

[22] Filed: Sept. 29, 1972 [21] Appl. No.: 293,719

Seiya Yamaguchi, Kanagawa. Japan [30] Foreign Application Priority DataSept. 30. 1971 Japan 46-76516 [52] U.S. Cl. 96/22; 96/60 BF [51] Int.Cl. G036 7/16; G03c 5/32 [58] Field of Search 96/60, 60 BF, 22

[56] References Cited UNITED STATES PATENTS 3.335.004 8/1967 Wrisley eta1 96/22 3.582.322 6/1971 Edens et al. 96/22 3.591.380 7/1971 Ohkubo eta1. I 6/22 3.667.950 6/1972 Amano ct a]. 96/22 3.741.763 6/1973 Amano ctal. 96/22 FOREIGN PATENTS OR APPLICATIONS 2.102.713 8/1972 Germany 96/60BF 1.190.855 5/1970 United Kingdom 96/60 BF OTHER PUBLICATIONS Mason.Processing Chemistry. 1966, pp. 210-211, 265-266.

Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-Sughrue,Rothwell. Mion, Zinn and Macpeak [57] ABSTRACT In a process forprocessing a color photographic material using a waterproof support, thestability of color images formed is remarkably improved by processingthe color photographic material, after color develop ment, in ablix-stabilizing bath containing a Fe (III)- organic acid complex salt,a solvent for silver halide, and a water-soluble compound having analdehyde group or a methylol group.

12 Claims, No Drawings COLOR PHOTOGRAPIIIC PROCESS BACKGROUND OF THEINVENTION 1. Field of the Invention The present invention relates to amethod for processing a color photographic material and moreparticularly to a color photographic process for forming stable colorphotographic images.

2. Description of the Prior Art It is well known in the colorphotographic field to form color photographic images by subjectingmultilayer color photographic materials; after exposure, to suchprocessings as development, bleaching, fixing, etc. Generally thesecolor photographic materials have, on one side of the support, threespectrally sensitized emulsion layers, i.e., a bluesensitive emulsionlayer, a green-sensitive emulsion layer, and a red-sensitive emulsionlayer. The color photographic materials have further, where appropriate,non-sensitive subsidiary layers such as a yellow filter layer, anantihalation layer, etc.

Each of the light-sensitive emulsion layers of the color photographicmaterials may contain a ketomethylene type coupler for forming yellowimages, a pyrazolone coupler for forming magenta images, or a phenolicor naphtholic coupler for forming cyan images.

The exposed multilayer color photographic materials are usuallysubjected, after color development, to a series of processings such asbleaching, fixing, water washing, etc., and then dried. Since itrequires a considerably long period of time for such a colorphotographic process, it has recently been desired to shorten theprocessing time and thus various attempts have been proposed for such apurpose. For instance, it has been proposed to shorten or simplify aconventional five-bath system composed of color development, fixing,bleaching, washing and stabilization steps by employing a blix step,that is, a step which combines the bleaching step and the fixing step.The three-bath system thus proposed is composed of a color development,blix, (washing) and stabilization step, and by employing such athree-bath system the color photographic processing period may beshortened to some extent as compared with the aforesaid five-bathsystem. However, even such a three-bath system requires a considerableprocessing time.

SUMMARY OF THE INVENTION An object of this invention is, therefore, toprovide a simplified and shortened photographic process for formingstable color photographic images.

The aforesaid object of this invention can be attained by processing acolor photographic material having a waterproof support, after colordevelopment, in a bath which simultaneously bleaches, fixes, andstabilizes the color photographic materials.

The novel blixstabilizing bath used in the process of this inventioncontains an oxidizing agent for silver, a solvent for silver halide, anda stabilizer for color images.

DETAILED EXPLANATION OF THE INVENTION As an oxidizing agent for silver,potassium ferricyanide is conventionally used for bleaching in theconventional five-bath system. However, the use of potassiumferricyanide is accompanied with disadvantages, i.e., it is difficult toform a stable system of potassium ferricyanide together with athiosulfate which is a solvent for silver halide, and the use ofpotassium ferricyanide causes problems of the waste liquid leading towater pollution. Accordingly, it is not appropriate to employ such aferricyanide in the blix-stabilizing bath of this invention. Therefore,in the process of this invention, a water-soluble ferric complex salt ofan organic acid is used as the oxidizing agent for silver. Such a ferriccomplex salt has the advantages that it is stable with a thiosulfate, isexcellent in chemical and photochemical stability, has less toxicity tohumans, and can be readily regenerated after use.

The organic acid capable of forming the watersoluble ferric complex saltof the acid used in this invention includes a compound represented bythe following general formula,

-COOH wherein X represents a hydrocarbon group, an oxygen atom, a sulfuratom, or

R R R R and R each represents a substituted or unsubstituted hydrocarbongroup; and R represents a hydrogen atom or a substituted orunsubstituted hydrocarbon group.

Specific examples of suitable organic acids are malonic acid, tartaricacid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid,thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid,ethylenediaminetetraacetic acid, aminotriacetic acid,ethylenedithioglycolic acid, dithioglycolic acid, and the like. Such anorganic acid readily forms a stable ferric chelate compound with atri-valent iron salt such as ferric chloride, ferric sulfate, or ironalum in an aqueous medium. Accordingly, in the present invention, theaforesaid organic acid may be used together with the tri-valent ironsalt in an aqueous medium or a ferric complex salt of the organic acidmay be used. Among them, the ferric complex salt of polyaminocarboxylic.acid, for example, ethylenediaminetetraacetic acid (EDTA), is mostgenerally used because such a complex salt has a high bleaching power,is stable and is easily obtained commercially.

The processing bath in this invention can also contain ableach-accelerator such as potassium bromide, potassium iodide, sodiumiodide, polyalkylene oxide, 2- mercaptoimidazole,3-mercapto-l,2,4-triazole, dithioglycol, a copper complex salt of anorganic acid such as cupric complex salt of EDTA, a cobalt complex saltof an organic acid such as cobaltic complex salt of EDTA, thiourea,ethylene thiourea, a selenium compound such as sodium selenosulfate,etc. Also, the processing bath can further contain ananti-bleach-fogging agent such as a hydroxylamine salt, p-aminophenol,hydroxymorpholine, ascorbic acid, l-phenyl-3- pyrazolidone,semicarbazide, hydrazine salt, etc.

As the fixing component for the blix-stabilizing bath in this invention,a silver halide solvent is employed. Examples of such solvents arethiosulfates such as sodium thiosulfate, ammonium thiosulfate, etc.,thiocyanates such as potassium thiocyanate, etc., sulfurcontainingorganic dibasic acids such as bisthioglycollic acid, etc., organic diolssuch as 3-thia-l,5-pentanediol, etc., and imidazolidine thion. Sodiumsulfite, etc., can be used in combination therewith as a fixing aid.

in order to find the compounds capable of being used together with theabove-mentioned bleaching component and fixing component and having thefunction of improving the stability of the color images, the inventorinvestigated the following compounds. That is to say, there areultraviolet absorbents such as water-soluble sulfo compounds, monoazocompounds, etc.; aldehyde compounds; combinations of aldehyde compoundsand ultraviolet absorbents or fluorescent brightening agents; cysteine;methylol; methylolbiuret; methylolurea; biuret derivatives as aredescribed in French Pat. No. 1,290,631; thiol compounds; polyhydroxycompounds; combinations of aldehydes and polycarboxylic acids;carbohydrazide; water-soluble salts of cysteine; water-soluble salts ofcopper, manganese, uranyl, nickel, lead, or zinc; glucoheptonic acid;glucoheptonate; glycine; glycylglycine; N,N-dialkylglycine; and adductsof aldehyde or methylketones and alkali metal sulfites.

As a result of the overall investigation of the systems resulting whenthe above compounds are used together with the bleaching component andthe fixing component indicated above, the stability of the solution, thefunction of stabilizing color images, the influence on the photographicproperties and physical properties of photographic materials, and thetoxicity to humans, it has been discovered that the water solublecompounds having an aldehyde group or a methylol group represented bythe general formula (I), (II), or (III) shown below are effective.

R-CHO General formula (I) OCH-R '-CHO wherein R represents a directbond, a divalent aliphatic group, or a divalent aromatic group.

Specific examples of compounds represented by general formula (II) areglyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde,glutaraldehyde, oz-methylglutaraldehyde, cyclopentane-dicarboxyaldehyde,and dialdehydes as disclosed in British Pat. No. 1,102,001 and FrenchPat. 1,543,694. The precursors of the above compounds such as2,5-dialkoxytetrahydrofuran, etc., described in Japanese Pat.Publication No. 27,570/'64 can also be used.

General formula (II) General Formula (lll) R" CH OH wherein R"represents an aliphatic group, an aromatic group, or a heterocyclicgroup.

Specific examples of the compounds represented by general formula (III)are N-methylolurea, N,N'- dimethylolurea, N-methylolmethylenebismonoethylurea, N'-methylol-N,N'-dimethylolurea, methylolhydantoin,dimethylolmelamine, monomethylol dimethylhydantoin,hydroxydimethylbiuret, trihydroxymethylbiuret,2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, compounds suchas 3-hydroxy- 2,2-dihydroxymethylpropionic acid, etc., described inBritish Pat. No. l,l [6,944, 2-nitroethanol derivatives such as2-nitro-2-methyl-l,3-propanediol described in Japanese Pat. applicationNo. 67,799/69, etc.

The novel blix-stabilizing bath used in the process of this inventioncontains, as fundamental components, the water-soluble ferric complexsalt of the organic acid, the solvent for silver halide, and thewater-soluble compound having an aldehyde group or a methylol group. Thediscovery of such a blix-stabilizing bath is quite astonishing onconsidering the difficulty of using an oxidizing agent such as awater-soluble ferric complex salt of an organic acid and a reducingagent such as formaldehyde simultaneously in a mono-processing bath.However, the inventors have succeeded in using the both components in astable manner effectively in a processing bath by adding a silver halidesolvent, such as sodium thiosulfate, to the system and adjusting the pHof the solution.

If the pH of the blix-stabilizing bath used in this invention is toolow, the bath is inferior in bleaching power and the stabilizing effectfor images and the density of the color images is sometimes reduced,while if the pH thereof is too high, the bleaching power is reduced. ThepH of it is suitably about 5.5 to about 7.5, preferably 6.0 to 7.0. Anyknown pH controlling agent may be used, but usually a carbonate isemployed for this purpose.

The amount of the water-soluble compound having an aldehyde group of amethylol group depends on the nature of the compound and is usuallydetermined upon considering the stabilizing effect for images and thestability of the solution. For instance, when a 37% aqueous solution offormaldehyde is employed, a preferred amount of the solution is 2 to 6ml per liter of the bath solution, while when 2% aqueous solution ofdimethylurea is employed, a preferred amount thereof is 4 to 15 ml perliter of the bath solution. ln general, a suitable amount of thewater-soluble compound having an aldehyde group or a methylol group isin the range of from 0.05 to 5 g per liter of the solution.

The amounts of the bleaching component and the fixing component areeasily determined according to the characteristics desired. Generallyfrom 40 to 60 g per liter of the bleaching component and from g to 200 gper liter of the fixing component, respectively, are employed.

Furthermore, a water-soluble fluorescent brightening agent can beincorporated in the blix-stabilizing composition of this invention toadd a color image stabilizing action and brightening action.

Also, a surface active agent may be incorporated in the bath compositionas a draining agent or an extender.

Any color photographic material such as a color photographic negativefilm, color photographic paper, reversal color photographic film, colorreversal paper, etc., can be used in the process of this invention.

In a color negative film and color reversal film, an anti-halationlayer, a red-sensitive emulsion layer containing a cyan coupler, agreen-sensitive emulsion layer containing a magenta coupler, a yellowfilter layer, a blue-sensitive emulsion layer containing a yellowcoupler, and a gelatin protective layer are formed on a support, in thisorder.

In a color photographic paper, a blue-sensitive emulsion layercontaining a yellow coupler, a greensensitive emulsion layer containinga magenta coupler, a red-sensitive emulsion layer containing a cyancoupler, and a gelatin protective layer are formed on a support, in thisorder.

Also, a packet-type color photographic material having a singlelight-sensitive layer having dispersed therein a packet containing ablue-sensitive emulsion and a yellow coupler, a packet containing agreensensitive emulsion and a megenta coupler, and a packet containing ared-sensitive emulsion and a cyan coupler can be used in the process ofthis invention.

In the present invention, the support for the color photographicmaterial must absorb no or substantially no water or photographicprocessing solution. Such supports are well known in this art aswaterproof or waterrepellent support. Examples of such supports arecellulose nitrate films, cellulose acetate films, polystyrene films,polycarbonate films, polyester films etc., and such films furthercontaining a white pigment, cellulose films opacified by dispersing afine foam therein as described in U.S. Pat. No. 2,422,008, a metallicsheet such as an aluminum sheet, baryta-coated papers havingincorporated in the paper pulp polygalactomannan as described in GermanPat. No. 1,262,756, supports composed of acyl cellulose fibers asdescribed in U.S. Pat. Nos. 3,098,786 and 3,132,944, and the socalledresin-coated papers prepared by coating both sides of a paper with awaterproof synthetic resin such as polyethylene, as described in U.S.Pat. No. 3,448,000, French Pat. No. 1,517,560, German Pat. Nos.1,261,746 and 1,809,606, and British Pat. No. 1,183,613. Ordinarybaryta-coated papers are unsuitable in the process of this inventionsince they require water washing for a long period of time to removechemicals absorbed therein during photographic processings.

The photographic layers applied onto the support may be any of theconventionally known ones. That is to say, as the hydrophilic colloidforming each of the photographic layers, there can be used gelatin,albumin, cellulose derivatives such as cellulose hydrates, polyvinylalcohol, etc. These photographic layers are preferably hardened byhardening agents. Known silver halide emulsions used in this invention.Each silver halide emulsion may contain, if desired, conventionaladditives such as a sensitizer, a sensitizing dye, a stabilizer, etc.

Moreover, the photographic materials used in thisinw-benzoylacet-(Z-n-pentadecyloxy)-4-sulfoanilide,

N-phenyl-N'-(p-acetaminophenol)-urea, ethyl-pbenzoylacetaminobenzenesulfonate, w-benzoylacet- 2,5-dichloroanilide,N,N'-di-(acetoacetamino)-3,3'-

dimethyldiphenyl, N-amyl-pbenzoylacetaminobenzene sulfonate.

Magenta couplers: l-phenyl-3-benzamidopyrazole-5-one,1-pnitrophenyl-3-n-amyl-5-pyrazolone, l-phenyl-3-acetylamino-S-pyrazolone, 2-cyanoacetyl-5 benzoylaminocoumarone, and 2-cyanoacetylcoumarone-S-sulfodimethylamide.

Cyan couplers:

l-stearoylamido4-( l '-hydroxy-2 '-naphthoylamido benzene-S-sulfonicacid, l-naphthol-5-sulfocyclohexylamide, 5-(n-benzyl-N-n-valerylamino l-naphthol, 2,4-dichloro-5-palmithylaminol -naphthol,2-benzoylamino-5-methylphenol, and 2,2'-dihydroxy-5.5-

' dibromostilbene.

These couplers can be incorporated into the hydrophilic colloid in anyconventional manner.

According to the process of this invention photographic materials are,after color development, processed in the blix-stabilizing bath and thenwashed and dried. As the color developing solution used for developingthe photographic materials, an alkaline aqueous solution containing aprimary aromatic amine developing agent is used. Any such conventionaldeveloping agent as used in present color developing processes may beused in the present invention. For example, there are illustratedphenylenediamine compounds and p-aminophenol compounds. Known additivesconventionally used in this field may be added to the developingsolution. For example, such additives as a sulfite, a bisulfite, acarbonate, a bromide, an iodide, an amine, benzyl alcohol, etc.

Of course, the processing steps of this invention vary to some extentaccording to the nature and use of the photographic materials to beprocessed as shown below. In the case of processing color negativefilms, after developing the color photographic films in a colordeveloping solution containing a color developing agent such as2-amino-5-diethylaminotoluene hydrochloride together with benzylalcohol, sodium metaborate, potassium bromide, etc., the photographicfilms are immediately processed in a stopping solution containingglacial acetic acid and, after washing, processed in theblix-stabilizing bath of this invention followed by washing and drying.

In the case of processing color photographic papers, after developingthe color photographic papers in a color developing solution containinga color developing agent such as p-hydroxyethylaminoaniline sulfatetogether with benzyl alcohol, sodium metaborate, hydroxylamine sulfate,sodium hydroxide, etc., the color photographic papers are immediatelywashed in a short period of time and then processed in theblix-stabilizing bath of this invention followed by washing and drying.

In the case of processing color reversal films or color reversal papers,after developing the color reversal materials in 'a black and whitedeveloping solution containing a developing agent such as metol,hydroquinone, and phenidone together with sodium carbonate, potassiumthiocyanide, potassium bromide, etc., the photographic materials areimmediately processed in a stopping solution containing glacial aceticacid, washed, subjected to a reversal exposure, subjected to colordevelopment in a color developing solution containing a color developingagent such as 2-amino-5- diethylaminotoluene hydrochloride together withbenzyl alcohol, sodium tertiary phosphate, sodium hydroxide,ethylenediamine, potassium bromide, etc., processed in theblix-stabilizing bath of this invention, washed, and then dried.

Now, the advantages obtained by the process of this invention will bedescribed in greater detail.

1. Reduction of the number of processing baths and shortage ofprocessing period of time:

As an example, in the case of using color photographic papers preparedby coating waterproof papers with the above-indicated photographicemulsions, the number of processing steps and the time required for eachstep in the conventional five-bath and three-bath system are comparedwith those in the two-bath system of this invention as shown in thefollowing table, in which the processing temperature is 24 C in eachstep.

Five-bath system Three-bath system Two-bath system 1. Color devel. Colordevel. Color development lopment lopment 6 min. 6 min. 6 min 2.Stop-fixing 2. Blixing 2. Blix-stabili- 2 min. 6 min. zation 6 min. 3.Washing 3. Washing 3. Washing 2 min. 3 min. 2 min. 4. Bleaching 4.Stabilization 2 min. 4 min. 5. Washing 2 min. 6. Hardeningfixing 4 min.7. Washing 3 min. 8. Stabilization 4 min. 8 steps 4 steps 3 steps 25min. 19 min. 14 min.

As is clear from the above table, the number of steps in the two-bathsystem of this invention is less than half of those in the five-bathsystem and is less than the number of the steps in the three-bath systemby one step. Furthermore, the processing time in the two-bath system ofthis invention is shortened about 40% as compared to the processingperiod in the five-bath system and about 25% as compared to theprocessing period in the three-bath system. Furthermore, in the processof this invention it is possible to finish the whole process withinminutes when the processing temperature is increased to 35 38 C.

Such a reduction in the number of processing baths and shortening of theprocessing time are quite effective to compactness the time required forprocessing in an automatic developing machine, to reduce the processingcost, increase the processing capacity, and increase the efficiency ofoperation.

2. Stabilization of the color images to heat, humidity, and light:

In the conventional systems a stabilization bath is employed before thedrying step as an independent step, but in the system of this inventiona stabilization effect similar to or better than that obtained by theconventional step is obtained by the processing in the blixstabilizationbath. That is to say, when the color paper processed according to theprocess described in Example 2 after stepwise exposure through a redfilter, a green filter, and a blue filter, and a color paper processedin the same way as in Example 2 except that only formalin was, removedfrom the blix-stabilizing composition, were placed for 10 days in achamber maintained at a temperature of 60 C and a humidity of 70%, thecolor densities, i.e., the cyan density, magenta density, and yellowdensity, of the color papers were measured, and compared. The yellow fogdensity of the paper processed in the bath containing formalin was 0.08,while that of the paper processed in the bath containing no formalin was0.12. This shows that the blix-stabilizing solution of this inventionprevents increased of yellow stain by heat and humidity with the passageof time.

Furthermore, when the above samples subjected to the describedprocessings were exposed to a xenon lamp for 12 hours, the yellowdensity of the sample obtained by the process using the processing bathcontaining no formalin was reduced to 0.87, while the yellow density ofthe sample processed in the processing solution containing formalin was1.00, which shows that the color image obtained with theblix-stabilizing bath was prevented from being faded by light.

An aldehyde compound is believed to stabilize unreacted couplers inemulsion layers by reaction with them and at the same time it isbelieved that it has the effect of preventing change of the color imagesdue to moisture by the hardening action thereof.

3. Prevention of the damage of films during processing and speed up ofdrying by the hardening action:

The emulsion layers softened during the development step, washing step,etc., are hardened again by the hardening action of the compound havingan aldehyde group or a methylol group in the blix-stabilizing bath andthus the emulsion layers are also prevented from being swollen in theblix-stabilizing bath and during washing. Therefore, the occurrence ofmechanical damage such as scratches, reticulation, etc., to the emulsionlayers during processing and washing can be effectively prevented.Furthermore, because the emulsion layers will not be melted by theaction of the hardening action even if the photographic materials areprocessed at a high temperature, it is possible to dry the photographicmaterial at high temperature in a shortened period of time.

4. Prevention of the generation of irritative gases:

In the conventional system of employing a stabilizing bath containingformalin, etc., directly before drying, irritative formalin vapors areformed during drying. Such a problem does not occur in the process ofthis invention since a washing treatment is conducted after theblix-stabilizing process.

The stabilization action for color images tends to be reduced when thewashing after the blix-stabilizing process is conducted for a longperiod of time but there is no such difficulty since in the process ofthis invention color photographic materials having waterproof supportsare employed.

Now, the invention will be described in greater detail by reference tothe following examples. Unless otherwise stated, all parts and percentsare by weight.

EXAMPLE 1 A polyethylene-coated waterproof paper prepared as ablue-sensitive silver iodobromide emulsion layer containingethyl-p-benzoylacetaminobenzene sulfonate, a green-sensitive silverchlorobromide emulsion layer containing1-p-nitrophenyl-3-n-amyl-5-pyrazolone, a red-sensitive silverchlorobromide emulsion layer containing2.4-dichloro-S-palmitylamino-l-naphthol, and a protective layer ofgelatin to provide a multilayer color photographic paper. Then the colorpaper was, after exposure, processed at 29.5 C in the following way:

Color development 6 min Washing 30 sec. Blix-stabilization 3 min Washing2 min Color developing solution:

Sodium tertiary phosphate (lIZH- O) g Sodium metaborate 10 g Anhydroussodium sulfite l g Hydroxylamine sulfate 2 g Potassium bromide 0.5 go-Nitrobenyjoimidazole nitrate (0.2%) ml Benzyl alcohol 40% solution 45ml Sodium hydroxide 1.2 g 4-Am ino-N-ethyl-N-(B-methasulfonamidoethyl)-mtoluidine sulfate 8.5 g Water to 1 liter pH10.0

Blix-stabilizing solution:

Ferric chloride 6H O 2.9 g Z-Sodium ethylenediaminetetraacetic acid 40 gAnhydrous sodium carbonate 16 g Anhydrous sodium thiosulfate 150 gAnhydrous sodium sulfite 10 g Formalin (37% formaldehyde) 4 ml Water tol liter pH 6.7

The processing time was shortened to about l2 minutes and the propertiesof the color image as well as the stability thereof to light and heatwere not inferior to those in a conventional system employing individualbleaching, fixing, and stabilizing steps.

EXAMPLE 2 In place of the blix-stabilizing solution used in Example l, asolution having the formula composition was used.

Ferric complex salt of EDTA Anhydrous sodium carbonate Anhydrous sodiumthiosulfate l Anhydrous sodium sulfite Formalin (37'71 formaldehyde)Water to Almost the same results as obtained in Example 1 were obtained.

EXAMPLE 3 In place of the blix-stabilizing solution used in Example l, asolution having the following composition was employed.

Ferric complex salt of EDTA 50 g Anhydrous sodium carbonate 6 gPotassium bromide l2 g Thiourea 10 g Ammonium thiosulfate 100 g TinopalGS 2 g Dimethylolurea (2% aqueous solution) 10 ml Water to 1 liter pH6.8 (C) mide Almost the same results as in Example 1 were obtained.

EXAMPLE 4 Color development 14 min. Stop 4 min. Wash 4 min.Blix-stabilization 12 min. Wash 6 min.

The composition of the color developing solution used in the aboveprocessings was the same as that described in Example 1.

Stop solution:

Glacial acetic acid 20 ml Anhydrous sodium sulfite l0 g Water to 1 literpH 4.5

Blix-stabilizing solution:

Ferric complex salt of EDTA 60 g Anhydrous sodium sulfite 10 g Anhydroussodium thiosulfate 200 g Anhydrous sodium carbonate 5 g Monomethyloldimethylhydantoin l g Water to 1 liter pH 6.5

The processing period of time was shortened and a color image stable tolight and heat was obtained.

While the invention has been described in detail and in terms ofspecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

l. A process for developing a color photographic material having awaterproof support wherein the material is subjected to a colordevelopment process and then simultaneously bleached, fixed andstabilized with an oxidizer, a silver halide solvent and a compoundcontaining an aldehyde group or a methylol group, wherein theimprovement consists essentially of color developing said material andthen simultaneously bleaching, fixing and stabilizing said photographicmaterial by processing the color photographic material in ablixstabilizing bath containing a water-soluble ferric complex salt ofan organic acid, a solvent for silver halide,

and 0.05 to 5.0 g. per liter of said bath of a watersoluble compoundhaving an aldehyde group or a methylol group and being selected from thegroup consisting of compounds represented by the formula RCHO wherein Rrepresents an alkyl group, an aryl group, an allyl group or aheterocyclic group, compounds represented by the formula Ol-lC-R'Cl-lOwherein R represents a direct bond, a divalent aliphatic group or adivalent aromatic group and compounds represented by the formula R"CH OHwherein R" represents an aliphatic group, an aromatic group, or aheterocyclic group, said blix-stabilizing bath having a pH within therange of about 5.5 to about 7.5.

2. The process of claim 1 wherein said water-soluble compound having analdehyde group or a methylol group is a compound represented by theformula RCHO wherein R represents an alkyl group, an aryl group, anally] group, or a heterocyclic group.

3. The process of claim 1 wherein said water-soluble compound having analdehyde group or a methylol group is a compound represented by theformula OHC-R'CHO wherein R represents a direct bond, a divalentaliphatic group or a divalent aromatic group.

4. The process of claim 1 wherein said water-soluble compound having analdehyde group or a methylol group is a compound represented by theformula R"-CH OH HOOC-R X-R COOH i 3.. LOOC R II R COOH HOOC-R -N-R COOHwherein X represents a hydrocarbon group, an oxygentetramethylolcyclohexanol,

atom, a sulfur atom, or a group; R R R R and R each represents asubstituted or unsubstituted hydrocarbon group; and R represents ahydrogen atom or a substituted or unsubstituted hydrocarbon group.

7. The process of claim 5, wherein said organic acid is malonic acid,tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolicacid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriaceticacid, ethylenediaminetetraacetic acid, aminotriacetic acid,ethylenedithioglycolic acid, or dithioglycolic acid.

8. The process of claim 1, wherein said solvent for silver halide is athiosulfate, a thiocyanate, an organic sulfur-containing dibasic acid,or an organic diol.

9. The process of claim 2, wherein said water soluble compound having aaldehyde group or a methylol group is formaldehyde, paraformaldehyde,trioxymethylene, glycolaldehyde, methylal, chloral, acetaldehyde, aldol,propiolaldehyde, acrolein, dibromoacrolein, crotonaldehyde,salicylaldehyde, gluoxylic acid, mucochloric acid, mucobromic acid,arabinose, xylose, glyceraldehyde, furfural or precursors thereof.

10. The process of claim 3, wherein said water soluble compound havingan aldehyde group or a methylol group is glyoxal, succinaldehyde,tartardialdehyde, terephthalaldehyde, glutaraldehyde,a-methylglutaraldehyde, cyclopentanedicarboxyaldehyde, or precursorsthereof.

11. The process of claim 4, wherein said water soluble compound havingan aldehyde group or a methylol group is N-methylolurea,N,N'-dimethylolurea, N- methylolmethylene bis-monoethylurea,N'-methylol- N,N'-dimethylolurea, methylohydantoin, dimethylolmelamine,monomethylol dimethylhydantoin, hydroxydimethylbuiret,trihydroxymethylbuiret, 2,2,6,6-

methyloldicyandiamide, 3-hydroxy-2,2-dihydroxymethylpropionic acid,2-nitro- 2-methyll ,3-propanediol.

12. The process of claim 1, wherein said blixstabilizing bathadditionally contains a water-soluble fluorescent brightening agent.

1. A process for developing a color photographic material having awaterproof support wherein the material is subjected to a colordevelopment process and then simultaneously bleached, fixed andstabilized with an oxidizer, a silver halide solvent and a compoundcontaining an aldehyde group or a methylol group, wherein theimprovement consists essentially of color developing said material andthen simultaneously bleaching, fixing and stabilizing said photographicmaterial by processing the color photographic material in ablix-stabilizing bath containing a water-soluble ferric complex salt ofan organic acid, a solvent for silver halide, and 0.05 to 5.0 g. perliter of said bath of a water-soluble compound having an aldehyde groupor a methylol group and being selected from the group consisting ofcompounds represented by the formula R-CHO wherein R represents an alkylgroup, an aryl group, an allyl group or a heterocyclic group, compoundsrepresented by the formula OHC-R''-CHO wherein R'' represents a directbond, a divalent aliphatic group or a divalent aromatic group andcompounds represented by the formula R''''-CH2OH wherein R''''represents an aliphatic group, an aromatic group, or a heterocyclicgroup, said blix-stabilizing bath having a pH within the range of about5.5 to about 7.5.
 1. A PROCESS FOR DEVELOPING A COLOR PHOTOGRAPHICMATERIAL HAVING A WATERPROFF SUPPORT WHEREIN THE MATERIAL IS SUBJECTEDTO A COLOR DEVELOPMENT PROCESS AND THEN SIMULTANEOUSLY BLEACHED, FIXEDAND STABILIZED WITH AN OXIDIZER, A SILVER HALIDE SOLVENT AND A COMPOUNDCONTAINING AN ALDEHYDE GROUP OR A METHYLOL GROUP, WHEREIN THEIMPROVEMENT CONSISTS ESSENTIALLY OF COLOR DEVELOPING SAID MATERIAL ANDTHEN SIMULTANEOUSLY BLEACHING, FIXING AND STABILIZING SAID PHOTOGRAPHICMATERIAL BY PROCESSING THE COLOR PHOTOGRAPHIC MATERIAL IN ABLIX-STABILIZING BATH CONTAINING A WATER-SOLUBLE FERRIC COMPLEX SALT OFAN ORGANIC ACID, A SOLVENT FOR SILVER HALIDE, AND 0.05 TO 5.0 G. PERLITER OF SAID BATH OF A WATER-SOLUBLE COMPOUND HAVING AN ALDEHYDE GROUPOR A METHYLOL GROUP AND BEING SELECTED FROM THE GROUP CONSISTING OFCOMPOUNDS REPRESENTED BY THE FORMULA R-CHO WHEREIN R REPRESENTS AN ALKYLGROUP, AN ARYL GROUP, AN ALLYL GROUP OR A HETEROCYCLIC GROUP, COMPOUNDSREPRESENTED BY THE FORMULA OHC-R''-CHL WHEREIN R'' REPRESENTS A DIRECTBOND, A DIVALENT ALIPHATIC GROUP OR A DIVALENT AROMATIC GROUP ANDCOMPOUNDS REPRESENTED BY THE FORMULA R" -CH2OH WHEREIN R" REPRESENTS ANALIPHATIC GROUP, AN AROMATIC GROUP, OR A HETEROCYCLIC GROUP, SAIDBLIXSTABILIZING BATH HAVING A PH WITHIN THE RANGE OF ABOUT 5.5 TO ABOUT7.5.
 2. The process of claim 1 wherein said water-soluble compoundhaving an aldehyde group or a methylol group is a compound representedby the formula R - CHO wherein R represents an alkyl group, an arylgroup, an allyl group, or a heterocyclic group.
 3. The process of claim1 wherein said water-soluble compound having an aldehyde group or amethylol group is a compound represented by the formula OHC-R''-CHOwherein R'' represents a direct bond, a divalent aliphatic group or adivalent aromatic group.
 4. The process of claim 1 wherein saidwater-soluble compound having an aldehyde group or a methylol group is acompound represented by the formula R''''-CH2OH wherein R'''' representsan aliphatic group, an aromatic group, or a heterocyclic group.
 5. Theprocess of claim 1 wherein the pH of said blix-stabilizing bath is inthe range of from 6.0 to 7.0.
 6. The process of claim 1, wherein saidorganic acid has the general formula HOOC-R1-X-R2-COOH or
 7. The processof claim 5, wherein said organic acid is malonic acid, tartaric acid,ethylmalonic acid, malic acid, fumaric acid, diglycolic acid,thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid,ethylenediaminetetraacetic acid, aminotriacetic acid,ethylenedithioglycolic acid, or dithioglycolic acid.
 8. The process ofclaim 1, wherein said solvent for silver halide is a thiosulfate, athiocyanate, an organic sulfur-containing dibasic acid, or an organicdiol.
 9. The process of claim 2, wherein said water soluble compoundhaving a aldehyde group or a methylol group is formaldehyde,paraformaldehyde, trioxymethylene, glycolaldehyde, methylal, chloral,acetaldehyde, aldol, propioLaldehyde, acrolein, dibromoacrolein,crotonaldehyde, salicylaldehyde, gluoxylic acid, mucochloric acid,mucobromic acid, arabinose, xylose, glyceraldehyde, furfural orprecursors thereof.
 10. The process of claim 3, wherein said watersoluble compound having an aldehyde group or a methylol group isglyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde,glutaraldehyde, Alpha -methylglutaraldehyde,cyclopentanedicarboxyaldehyde, or precursors thereof.
 11. The process ofclaim 4, wherein said water soluble compound having an aldehyde group ora methylol group is N-methylolurea, N,N''-dimethylolurea,N-methylolmethylene bis-monoethylurea,N''-methylol-N,N''-dimethylolurea, methylohydantoin, dimethylolmelamine,monomethylol dimethylhydantoin, hydroxydimethylbuiret,trihydroxymethylbuiret, 2,2,6,6-tetramethylolcyclohexanol,methyloldicyandiamide, 3-hydroxy-2,2-dihydroxymethylpropionic acid,2-nitro-2-methyl-1,3-propanediol.